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The dynamic motion of a M (M = Ca, Yb) atom inside the C74 (D 3h) cage: a relativistic DFT study

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Abstract

The interaction between M (M = Ca, Yb) atom and C74 (D 3h) has been investigated by all electron relativistic density function theory. With the aid of the representative patch of C74 (D 3h), we studied the interaction between C74 (D 3h) and M (M = Ca, Yb) atom and obtained the interaction potential. Optimized structures show that there are three equivalent stable isomers and there is one transition state between every two stable isomers. According to the minimum energy pathway, the possible movement trajectory of M (M = Ca, Yb) atom in the C74 (D 3h) cage is explored. The calculated energy barrier for Yb atoms moving from the stable isomer to the transition state is 10.4 kcal mol−1 and the energy barrier for Ca atoms is 6.1 kcal mol−1. The calculated NMR spectra of M@C74 (M = Ca, Yb) are in good agreement with the experimental data. There are nine lines in the spectra: one 1/6 intensity signal, four half intensity signals and four full intensity signals.

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References

  1. Heath JR, O’Brien SC, Zhang Q, Liu Y, Curl RF (1985) Lanthanum complexes of spherical carbon shells. J Am Chem Soc 107:7779–7780

    Article  CAS  Google Scholar 

  2. Chai Y, Guo T, Jin C, Haufler RE, Chibante LPF (1991) Fullerenes with metals inside. J Phys Chem 95:7564–7568

    Article  CAS  Google Scholar 

  3. Nikawa H, Kikuchi T, Wakahara T, Nakahodo T, Tsuchiya T (2005) Missing metallofullerene La@C74. J Am Chem Soc 127(27):9684–9685

    Article  CAS  Google Scholar 

  4. Xu J, Takahiro T, Hao C, Shi Z, Wakahara T (2006) Structure determination of a missing-caged metallofullerene: Yb@C74 (II) and the dynamic motion of the encaged ytterbium ion. Chem Phys Lett 419:44–47

    Article  CAS  Google Scholar 

  5. Haufe O, Reich A, Moschel C, Jansen M (2001) Darstellung, Isolierung und Charakterisierung von Ba@C74. Z. Anorg Allg Chem 627:23–27

    Article  CAS  Google Scholar 

  6. Grupp A, Haufe M, Jansen M, Mehring M, Panthofer J (2002) Synthesis, isolation and characterisation of New alkaline earth endohedral fullerenes M@Cn (M = Ca, Sr; n = 74, 76). AIP Conference Proceedings 633:31–34

    Article  CAS  Google Scholar 

  7. Haufe O, Hecht M, Grupp A, Mehring M, Jansen M (2005) Isolation and spectroscopic characterization of new endohedral fullerenes in the size gap of C74 to C76. Z Anorg Allg Chem 631:126–130

    Article  CAS  Google Scholar 

  8. Kuran P, Krause M, Bartl A, Dunsch L (1998) Preparation, isolation and characterisation of Eu@C74:the first isolated europium endohedral fullerene. Chem Phys Lett 292:580–586

    Article  CAS  Google Scholar 

  9. Okazaki T, Lian Y, Gu ZN, Suenagac K, Shinohara H (2000) Isolation and spectroscopic characterization of Sm-containing metallofullerenes. Chem Phys Lett 320:435–440

    Article  CAS  Google Scholar 

  10. Okazaki T, Suenaga K, LianY GZ, Shinohara H (2001) Intrafullerene electron transfers in Sm-containing metallofullerenes:Sm@C2n (74 ≤ 2n ≤ 84). J Mol Graph Model 19:244–251

    Article  CAS  Google Scholar 

  11. Okazaki T, Suenaga K, Lian YF, Gu ZN, Shinohara H (2000) Direct EELS observation of the oxidation states of Sm atoms in Sm@C2n metallofullerenes (74 ≤2n ≤84). J Chem Phys 113:9593–9597

    Article  CAS  Google Scholar 

  12. Wan TSM, Zhang HW, Nakane T (1998) Production, isolation, and electronic properties of missing fullerenes:Ca@C72 and Ca@C74. J Am Chem Soc 120:6806–6807

    Article  CAS  Google Scholar 

  13. Xu JX, Lu X, Zhou XH, He XR, Shi ZJ (2004) Synthesis, isolation, and spectroscopic characterization of ytterbium-containing metallofullerenes. Chem Mater 16:2959–2964

    Article  CAS  Google Scholar 

  14. Dinadayalane TC, Leszczynski J (2010) Remarkable diversity of carbon–carbon bonds: structures and properties of fullerenes, carbon nanotubes, and grapheme. Struct Chem 21:1155–1169

    Article  CAS  Google Scholar 

  15. Miyake Y, Suzuki S, Kojima Y, Kikuchi K, Kobayashi K (1996) Motion of scandium ions in Sc2C84 observed by 45Sc solution NMR. J Phys Chem 100:9579–9581

    Article  CAS  Google Scholar 

  16. Nishibori E, Takata M, Sakata M, Tanaka H, Hasegawa M (2000) Giant motion of La atom inside C82 cage. Chem Phys Lett 330:497–502

    Article  CAS  Google Scholar 

  17. Kodama T, Fujii R, Miyake Y, Suzuki S, Nishikawa H (2004) 13C NMR study of Ca@C74: the cage structure and the site-hopping motion of a Ca atom inside the cage. Chem Phys Lett 399:94–97

    Article  CAS  Google Scholar 

  18. Yamada M, Wakahara T, Nakahodo T, Tsuchiya T, Maeda Y (2006) Synthesis and structural characterization of endohedral pyrrolidinodimetallofullerene: La2@C80(CH2)2NTrt. J Am Chem Soc 128:1402–1403

    Article  CAS  Google Scholar 

  19. Umemoto H, Ohashi K, Inoue T, Fukui N, Sugai T (2010) Synthesis and UHV-STM observation of the T d-symmetric Lu metallofullerene: Lu2@C76(T d). Chem Commun 46:5653–5655

    Article  CAS  Google Scholar 

  20. Andreoni W, Curioni A (1996) Freedom and constraints of a metal atom encapsulated in fullerene cages. Phys Rev Lett 77:834–837

    Article  CAS  Google Scholar 

  21. Vietze K, Seifert G, Fowler PW (2000) Structure and dynamics of endohedral fullerenes. AIP Conf Proc 544:131–134

    Article  CAS  Google Scholar 

  22. Heine T, Vietze K, Seifert G (2004) 13C NMR fingerprint characterizes long time-scale structure of Sc3N@C80 endohedral fullerene. Magn Reson Chem 42:S199–S201

    Article  CAS  Google Scholar 

  23. Jin P, Hao C, Li SM, Mi WH, Sun ZC (2006) Theoretical study on the motion of a La atom inside a C82 cage. J Phys Chem A 111:167–169

    Article  Google Scholar 

  24. Zhang JF, Hao C, Li SM, Mi WH, Jin P (2007) Which configuration is more stable for La@C80, D3d or D2h? recompution with ZORA methods within ADF. J Phys Chem C 111:7862–7867

    Article  CAS  Google Scholar 

  25. Gan LH, Chang Q, Zhao C, Wang CR (2013) Sc2S@C74: Linear metal sulfide cluster inside an IPR-violating fullerene. Chem Phys Lett 570:121–124

    Article  CAS  Google Scholar 

  26. Gan LH, An J, Pan FS, Chang Q, Liu ZH, Tao CY (2011) Geometrical and electronic rules in fullerene-based compounds. Chem Asian J 6:1304–1314

    Article  CAS  Google Scholar 

  27. Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys 92:508–517

    Article  CAS  Google Scholar 

  28. Delley B (1990) From molecules to solids with the DMol3 approach. J Chem Phys 113:7756–7764

    Article  Google Scholar 

  29. Artacho E, Sànchez-Portal D, Ordejòn P, Garcla A, Soler JM (1999) Linear-scaling ab-initio calculations for large and complex systems. Phys Status Solidi (a) 215:809–817

    Article  CAS  Google Scholar 

  30. Becke AD (1998) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100

    Article  Google Scholar 

  31. Lee C, Yang W, Parr RG (1998) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789

    Article  Google Scholar 

  32. Powell RE (1968) Relativistic quantum chemistry. J Chem Educ 45:558–563

    Article  CAS  Google Scholar 

  33. Pitzer K (1979) Relativisitic effects on chemical properties. Acc Chem Res 12:271–276

    Article  CAS  Google Scholar 

  34. Pyykko P, Desclaux JP (1979) Relativity and the periodic system of elements. Acc Chem Res 12:276–281

    Article  CAS  Google Scholar 

  35. Halgren TA, Lipscomb WN (1997) The synchronous-transit method for determining reaction pathways and locating molecular transition states. Chem Phys Lett 49:225–232

    Article  Google Scholar 

  36. Guerra CF, Snijders JG, te Velde G, Baerends EJ (1998) Towards an order-N DFT method. Theor Chem Acc Theory Comput Model (Theoretical Chimica Acta) 99:391–403

    CAS  Google Scholar 

  37. te Velde G, Bickelhaupt FM, Baerends EJ, Guerra CF, van Gisbergen SJA (2001) Chemistry with ADF. J Comput Chem 22:931–967

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21036006 and 21137001).

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  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, People’s Republic of China

    Wei Zheng, Suzhen Ren, Dongxu Tian & Ce Hao

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  1. Wei Zheng
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  2. Suzhen Ren
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  3. Dongxu Tian
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  4. Ce Hao
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Correspondence to Ce Hao.

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Zheng, W., Ren, S., Tian, D. et al. The dynamic motion of a M (M = Ca, Yb) atom inside the C74 (D 3h) cage: a relativistic DFT study. J Mol Model 19, 4521–4527 (2013). https://doi.org/10.1007/s00894-013-1958-x

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  • DOI: https://doi.org/10.1007/s00894-013-1958-x

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